1-hydroxy-2-naphthamide colored couplers



Patented Sept. 12, 1950 COUPLERS Dndley-EHGrlass, Paul W. Vitturn, andArnold Weissherger, {Roche-aster, N. 1 'assignors to Eastman KodakCompany; "Rochester, NI'YJ a corporation cf New Jersey N 0 Drawing.Application March 13, 1947,

' Serial No. 734,548

10 Claims.

.1 This invention relates to color photography and particularly to colorcouplers for use in photographic processes.

Color-forming compounds which react with the development product ofaromatic amino developing agents to form colored images "uponphotographic development'are well known. Generally, thesecolor-forming-compounds of couplers are colorless or substantiallycolorless. This lack of color is usually desirable where the coupler isto be incorporated in'the. emulsion layer and the unused coupler remainsafter'formation of the colored image. When the coupler is used in thedeveloping'solution,it may be colored without detriment to the finalimage" and certain colored couplers have been used in this way.

In our prior application Serial No. 533931, filed May 3, 1944, nowPatentNo. 2,455,169, of which the present application is acontinuationin-part, we have described couplers having the generalformula in which R is a benzene or naphthalene nucleus which has the=azogroup in a position para to the hydroxyl group and R an aromatic orheterocyclic radical. 'These -couplers are in them selves more or lessstrongly colorecLand during the coupling reaction, the chromophoresystem in the coupler is destroyed or split off with the.

result that the-original color of the coupler is destroyed and a new dyeis formed upon coupling. Thus on developing an emulsion layer containingone of these colored couplers, the coupler color is destroyed-and a newcolor is formed by the coupling reaction :at thosepoints wheredevelopment occurs. There-is formed in-thisway a dye image of one coloron, 'abaclz gro-und of another color.

We have now found a class of colored couplers to orange-red in color andyield cyan or bluegreen dyes by reaction with the oxidizedd'eveloD- ingagent.

The'couplers'yvhich we proposeto use according to the present inventionhave thefollowinfg general formula: p

I T N- B especially \a'mononuclear aryl radical such as phenyl orsubstituted phenyl, a mononuclear aryloxyphenyl radical such asp-tertiary-butylphenoiryphenyl, p-tert.-amylphenoxyphenyl, 2,4-

d-iamylnhenoxyphenyl or phenoxypnenyl or an active po'sitionof thecoupler, issubstituted with an azo group --and this .group is split offior removed by the oxidized developer when thea'zosubstituted coupler istreated with the-oxidized developer either in aqueous solution or in thephotographic emulsion layer. Thus the coupler may be converted to adifierently colored compound and the azo .group readily -removed;trom itby means oi :reaction wi-th the oxidized deasarpoa OOllehydroxy-l-phenylazo-N-isoamyl-2maphthanilide 1-hydroxy-4- (2metl1oxy-4-nitrophenylazo -N-is0amyl- 2-naphthanilide 3 C H3 00 Ha1-hydroxy-4- [Z-methoxyl- (o-methoxyphenylazo) phenylazo]-N-isoamyl2-naphthanilide Our compounds may be incorporated either inthe developing solution or in the emulsion layer according to theirintended use and diffusion characteristics. Generally, they will be usedin one of the emulsion layers of a multi-layer coating in order tosecure the masking effects described in Hanson U. S. application SerialNo. 533,910, filed May 3, 1944, now Patent. No. 2,449,966. The Hansonprocess involves a color correction method in which a color coupler isincorporated in the photographic emulsion layer prior to exposure andupon development is con.- verted to a colored image where theJayer iseX-- posed. The coupler remaining in the: unexposedportions of the layerretains itsv original color and by suitable choiceof the coloroftheoriginal coupler and the color of the final dye image, a masking orcorrection effect can be obtained.

The compounds employed according to our invention may be prepared by anysuitable method such as by reaction of the naphthamide with theappropriate diazonium compound. For example, compound No. 1 was preparedas follows:

1. l hydroxy 4' (p-tert. butylphenoxy) -2- naphthanilide was prepared bythe condensation of equi-molecular quantities of phenyll-hydroxy-2-naphthoate and p-(p-tert-butylphenoxy-) -aniline at 200 forone hour. The product was purified by recrystallizationfrom a mixture ofbenzene and ligroin.

The p (p-tert.-butylphenoxy) aniline was prepared by alkali condensationof hot p-nitro chlorobenzene and p-tert-butylphenol followed bycatalytic reduction of the nitro compound in the presence of Raneynickel.

1 hydroxyl-phenylazo-' (p-tert.-butylphenoXy)-2-naphtl'1anilide (1) wasprepared by adding an aqueous solution of 1.05 moles ofrben-.- zenediazonium chloride to one mole of l-hydroxy 4 (p-tert.-butylphenoxy) 2naphthanilide dissolved in eight liters of pyridineethanol (1-1)solution at- 5 C'. The product is isolated by pouring the mixturev intoan excess 6 Q ofzdilute hyd'rochloric.acid. The pure.adye.:is..ob tainedby crystallization from. dioxane or acetic acid.

Compounds 2 to v5. wereprepared. in the same mannerascompound l usingthe following couplers and diazonium salts.

Coupler Diazonium salt o-methoxybenz-ene diazonlum chloride. paoetamldobenzene noxy) 2 naphthanilide. diazonium chloride. 4'1-hydroxy-4-(p-tert.-butylphe- Z-meth o xylenitronoxy) -2-naphthanilide.benzene diazonium f chloride. 5.----- l-hydroxy-4'- (p-tert.-butylpl1e-2-n1ethoxy4-pl1enylnoxy) -2-naphtlianilide. azobenzene diazoniumchloride.

Compound No. 6 was: prepared as follows:

6. lg-hydroxy l (p-tert-.-amylphenoxy)- 2+naphthanilidewas, prepared: bythe condensation at-room temperature: of on equivalent of1+hydroxy-2-naphthoyl chloride with two equivalents of 4- ('p' tert.amylphenoxy) aniline in ether. The amine hydrochloride was removed byfiltration and the filtratewas concentrated toacrude product which wasrecrystallized from amixture of ligroin and benzene.

The ,4- (p-tert-.-amylphenoxy-)aniline was preparedby the condensationof hot p-nitrochlorobenzene and p-terteamylphenol in alkali to yield 4(p tert. amylphenoxy)nitrobenzene. The nitro compound was reducedcatalytically in' the presence of Raney nickel to-4-(=p-tert.-amylphenoxy) aniline.

1-- hydroxy--(o met-hoxyphenylazo)-4'-(ptert.amylphenoxy)-2-naphthanilide (6) was prepared by adding an equivalentsolution of 1.05 mols of omethoxybenzene diazonium chloride to 1 mol of1hydroxy-4-(p-tert.-amy1phenoxy)-2- naphthanilide in 8 liters ofpyridine ethanol (1:1) solution at 5 C. The product was isolated bypouring the mixture into an excess of hydrochloric acid. The pure dyewas obtained by crystallization from dioxane or acetic acid.

Compound No. '7 was prepared as follows:

1 hydroxy-J-(2,4-diamylphenoxy) -2-naphthanilide was prepared in amanner similar to 1 hydroxy-4 -(p-tert.-butylphenoxy) -2-naphthanilide,which was used in the preparation of compound No. 1, by using p (2,4diamylphenoxy aniline instead of p (p-tert-butylphenoxy) aniline.

1- hydroxy-4- (p-br-omophenylazo) -4- (2,4-diamylphenoxy) 2naphthanilide was prepared by treating l-hydroxy-4- (ZA-diamylphenoxy)Z-naphthanilid'e with p-bromobenzene diazonium chloride.

Compound No. 8 was prepared in the following manner:

8. l hydroXy-N {4-['2-(2A-diamylphenoxy)- 5-3.5-dichloro-sulfamylbenzamido) benzarnidol phen'ethyl}-2-naphthamidewas prepared by the following steps:

(a) Phenyl l-hydroxy-Z-naphthoate was condensed at for one-half hourwith an equimolecular quantity of p-nitrophenethylamine yielding 1hydroXy-N-(p-nitrophenethyl) 2- naphthamide.

(b) The nitro compound was reduced catalytically in the presence ofRaney nickel to the amine.

(c) 1.- hydroxy -.N (p-ami'nophenethyll-Z- naphthamide. was condensed inacetic acid and sodium acetate at room temperature with an equimolecularquantity of 2 (2,4 diamylphenoxy) --nitrobenzoyl chloride.

(d) l-hydroxy-N-{4-[2- (2,4-diamylphenox'y) 5aminobe'nzamido]phenethy1}-2-naphthamide was prepared by the catalyticreduction in the presence of Raney nickel of the nitro compound obtainedin step (c).

(e) 1 hydroxy N {4.- [2 (2,4 diamylphenoxy) 5(3,5-dichlorosulfonybenzamido)- benzamido]phenethyl}-2-naphthamide wasprepared by th condensation of an equimolecular quantity of3,5-dichlorosul fonyl benzoyl chloride and the amine of step (d) indioxane and qinoline.

The final compound was prepared by the simple treatment of 1 hydroxy-N-{i-[2-(2,4-diamylphenoxy) 5-(3,5-dichlorosulfonylbenzamido) benzamido]phenethyl}2-naphthamide with benzene diazonium chloride.

Compound 9 was prepared by the condensation in ether of two equivalentsof N-methylaniline with 1 equivalent of l-hydroxy-Z-naphthoyl chlorideto produce l-hydroxy-N-methyl- 2-naphthanilide. The final compound wasprepared by treating this intermediate with o-carbethoXy-benzenediazonium chloride.

Compound 10 Was prepared by the condensation in ether of 2 equivalentsof N-isoamylaniline with 1 equivalent of 1-hydroxy-2-naphthoyl chlorideto produce l-hydroxy-N-isoamyl-Z- naphthanilide. This intermediate wastreated with benzene diazonium chloride to produce the final compound.

Compounds 11 and 12 were prepared similarly to compound 10 by treatingl-hydroxy-N-isoamyl-Z-naphthanilide with the appropriate diazonium saltas follows:

Coupler Diazonium salt Z-meth oxyA-nitrobenzene diazonium chloride.

Z-rnethoxyi- (o-methoxyphenyl-azo) benzene diazonium chloride.

l-hydroxy-N-isoamyl-Z-naphthanilide.

l-hydroxy-N-isoamyl-2-naphthanilide.

Various photographic developing agents can be employed with the couplersof our invention.

The primary aromatic amino developing agents are generally suitableincluding the phenylenediamines and aminophenols. The alkylphenylenediamines may be substituted in the amino group as well as inthe ring. Suitable compounds Grams 2-amino-5-diethyl-amino toluene HCl 2Sodium sulphite 2 Sodium carbonate Potassium bromide 2 Water .to V1liter.

It will be understood that the examples and,

where X is selected from the class consisting of hydrogen and alkylradicals, Y is selected from the class consisting of mononuclear arylradicals and aralkyl radicals and R is a mononuclear aryl radical.

2. The method of developing a colored image in a silver halide emulsionlayer which comprises incorporating in said layer' a coupler compoundhaving the formula:

Where X is selected from the class consisting of hydrogen and alkylradicals, Y is selected'from the class consisting of mononuclear arylradicals and aralkyl radicals and R is a mononuclear aryl radical,exposing said layer and developing it with a primary aromatic aminodeveloping agent, thereby splitting oil the N='NR, group in said couplercompound and coupling said compound at the point of splitting with theoxidation prodnot of the primary aromatic amino developing agent to forma dye image.

3. The method of developing a colored image in a silver halide emulsionlayer which comprises incorporating in said layer a coupler compoundhaving the formula:

where Y is a mononuclear aryl-oxyphenyl radical and R is a mononucleararyl radical, exposing said layer and developing it with a primaryaromatic amino developing agent, thereby splitting oi'i the N=NR groupin said coupler compound and coupling said compound at the point ofsplitting with the oxidation product of the primary aromatic aminodeveloping agent to form a dye image.

4. The method of developing a colored image n a silver halide emulsionlayer which comprises incorporating in said layer a coupler compoundhaving the formula:

I CH

exposing said layer and developing it with a primary aromatic aminodeveloping agent, thereby splitting 01f the group in said couplercompound and coupling said compound at the point of splitting with theoxidation product of the primary aromatic amino developing agent to forma dye image.

5. The method of developing a colored image in a silver halide emulsionlayer which comprises incorporating in said layer a coupler compoundhaving the formula:

C ON

exposing said layer and developing it with a primary aromatic aminodeveloping agent, thereby splitting 01f the group in said couplercompound and coupling said compound at the point of splitting with theoxidation product of the primary aromatic amino developing agent to forma, dye image.

6. A gelatino silver halide emulsion layer containing a coupler compoundhaving the formula:

N=NR

where X is selected from the class consisting of hydrogen and alkylradicals, Y is selected from the class consisting of mononuclear arylradicals, aralkyl radicals and R is a mononuclear aryl radical.

7. A gelatino silver halide emulsion layer containing a coupler compoundhaving the formula:

O ONH-Y N=NR Where Y and R are mononuclear aryl radicals.

a 8. A gelatino silver halide emulsion layer containing a couplercompound having the formula:

O ONH-Y where Y is a mononuclear aryloxyphenyl radical and R is amononuclear aryl radical.

9. A gelatino silver halide emulsion layer containing a coupler compoundhaving the formula:

O OK CH3 1 O N=N 10. A gelatino silver halide emulsion layer containinga, coupler compound having the formula:

C O N- 5 DUDLEY B. GLASS.

PAUL W. VITTUM. ARNOLD WEISSBERGER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

1. THE METHOD OF DEVELOPING A COLORED IMAGE IN A SILVER HALIDE EMULSIONLAYER WHICH COMPRISES EXPOSING SAID EMULSION LAYER AND DEVELOPING ITWITH A PRIMARY AROMATIC AMINO DEVELOPING AGENT IN THE PRESENCE OF ACOUPLER COMPOUND HAVING THE FORMULA: